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WO2004072137A1 - Polymeres modifies par du caoutchouc obtenus a partir de monomeres aromatiques vinyliques - Google Patents

Polymeres modifies par du caoutchouc obtenus a partir de monomeres aromatiques vinyliques Download PDF

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Publication number
WO2004072137A1
WO2004072137A1 PCT/US2004/002890 US2004002890W WO2004072137A1 WO 2004072137 A1 WO2004072137 A1 WO 2004072137A1 US 2004002890 W US2004002890 W US 2004002890W WO 2004072137 A1 WO2004072137 A1 WO 2004072137A1
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WIPO (PCT)
Prior art keywords
rubber
functionalized
polymer
grafted
matrix polymer
Prior art date
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Ceased
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PCT/US2004/002890
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English (en)
Inventor
Michael O. Myers
Mehmet Demirors
Bruce A. King
Mercedes R. Galobardes
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to AT04707710T priority Critical patent/ATE455809T1/de
Priority to EP04707710A priority patent/EP1592723B1/fr
Priority to BR0406505-0A priority patent/BRPI0406505A/pt
Priority to MXPA05008344A priority patent/MXPA05008344A/es
Priority to US10/542,681 priority patent/US20060247375A1/en
Priority to CA002513648A priority patent/CA2513648A1/fr
Priority to DE602004025203T priority patent/DE602004025203D1/de
Priority to JP2006503242A priority patent/JP2006516672A/ja
Publication of WO2004072137A1 publication Critical patent/WO2004072137A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C08F290/128—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • This invention relates to rubber modified polymers produced from vinyl aromatic monomers.
  • Rubber-modified polymers such as high impact polystyrene (HIPS) and acrylonitrile/butadiene/styrene (ABS) are typically produced by polymerizing styrene or styrene/acrylonitrile in the presence of a dissolved rubber, such that the rubber is dispersed within the polymer matrix in the form of discrete rubber particles containing occluded matrix polymer therein.
  • the physical properties of the rubber modified polymer can be enhanced with grafted rubber, particularly with increased levels of grafting.
  • matrix polymers are grafted onto the rubber backbone.
  • certain initiators such as peroxide initiators, can be used which abstract hydrogen atoms from the rubber polymer backbone.
  • this method may also cause increased reactivity, making the reaction difficult to control.
  • Another approach involves generating SO in a rubber/styrene mixture by heating a compound which releases SO, such as bisquinone peroxide as described in U.S. 4,895,907 by Priddy et al.
  • SO such as bisquinone peroxide
  • U.S. 4,895,907 by Priddy et al.
  • a compound which releases SO such as bisquinone peroxide as described in U.S. 4,895,907 by Priddy et al.
  • SO sulfur trihenylphosphite ozonides
  • to increase the grafting onto a polybutadiene rubber for the preparation of polybutadiene- modified polystyrene, as disclosed in "Polybutadiene Hydroperoxide by Singlet Oxygen: Its Grafting and Morphology in Polystyrene Matrix", Journal of Applied Polymer Science, Vol. 31, 1827-1842 (1986) by Peng.
  • the process described does not achieve high levels of grafting
  • U.S. 5,959,033 discloses a method of producing highly grafted rubber in high impact styrene polymers using SO by decomposition of phosphite ozonides in the vinyl aromatic monomer and rubber feed of a mass polymerization process, such that at least 30 percent grafting is achieved at the point of phase inversion.
  • this process requires the additional ozonide reactant and adds complexity to the reaction process.
  • the present invention is a rubber modified polymer comprising a) a polymer matrix comprising a polymerized vinyl aromatic monomer, and b) a grafted rubber, dispersed within the polymer matrix in the form of discrete rubber particles containing occluded matrix polymer therein, wherein the grafted rubber is characterized by: i) a degree of grafting of from 30 to 100 percent at the point of phase inversion, ii) an amount of matrix polymer grafted to the rubber of from 20 to 75 weight percent of the total amount of matrix polymer, and iii) being produced by reacting the matrix polymer with a functionalized rubber, wherein the functional group is capable of reacting with the matrix polymer under polymerization conditions, thus grafting the matrix polymer to the rubber.
  • This rubber modified polymer containing highly grafted rubber combined with the defined graft/matrix ratio has enhanced physical properties and economic advantage when compared to rubber modified polymers of the prior art.
  • Another aspect of the present invention is a process for producing such rubber modified polymers comprising a matrix polymer having dispersed discrete rubber particles containing occlusions of matrix polymer therein, wherein the process comprises: a) polymerizing a vinyl aromatic monomer in the presence of a functionalized rubber containing a functionality which is capable of reacting with the matrix polymer, such that at least 30 percent of the functionalized rubber is grafted with matrix polymer at the point of phase inversion.
  • This process allows for the efficient and cost effective production of rubber modified polymers containing highly grafted rubbers without the deficiencies of the prior art.
  • the rubber modified polymers of the present invention comprise a matrix polymer, and a grafted rubber.
  • Matrix polymer is grafted to a functionalized rubber, which is dispersed throughout the remaining matrix polymer in the form of discrete rubber particles containing occlusions of matrix polymer therein.
  • the matrix polymer can be any polymer produced from a vinyl aromatic monomer.
  • Suitable vinyl aromatic monomers include, but are not limited to, those vinyl aromatic monomers known for use in polymerization processes, such as those described in U.S. patents 4,666,987, 4,572,819 and 4,585,825.
  • the monomer is of the formula:
  • Ar is an aromatic ring structure having from 1 to 3 aromatic rings with or without alkyl, halo, or haloalkyl substitution, wherein any alkyl group contains 1 to 6 carbon atoms and haloalkyl refers to a halo substituted alkyl group.
  • Ar is phenyl or alkylphenyl, wherein alkylphenyl refers to an alkyl substituted phenyl group, with phenyl being most preferred.
  • Typical vinyl aromatic monomers which can be used include: styrene, alpha-methylstyrene, all isomers of vinyl toluene, especially paravinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, vinyl anthracene, and mixtures thereof.
  • the vinyl aromatic monomers may also be combined with other copolymerizable monomers.
  • Such monomers include, but are not limited to acrylic monomers such as acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, acrylic acid, and methyl acrylate; maleimide, phenylmaleimide, and maleic anhydride.
  • Impact modified, or grafted rubber containing products are additionally described in USP's 3,123,655; 3,346,520; 3,639,522; and 4,409,369.
  • the weight average molecular weight (Mw) of the matrix polymer is typically 50,000 to 500,000, preferably 60,000 to 400,000 and most preferably 80,000 to 350,000.
  • the grafted rubber comprises a rubber substrate containing grafts of the matrix polymer, obtained by reacting the matrix polymer with the functional group of the functionalized rubber.
  • the functionalized rubber can be any unsaturated functionalized rubbery polymer having a glass transition temperature of not higher than 0°C, preferably not higher than -20°C, as determined by ASTM D-756-52T, containing at least 1 functional group per rubber molecule, wherein the functional group(s) is capable of reacting with the matrix polymer under polymerization conditions.
  • the functionalized rubber suitable for the present invention are those that have a solution viscosity in the range of 5 to 300 cps (5 percent by weight styrene at 20° C) and Mooney viscosity of 5 to 100 (ML+1, 100° C).
  • Suitable rubbers include, but are not limited to, functionalized diene rubbers, butyl rubbers, ethylene-propylene-diene monomer (EPDM) rubbers, and silicone rubbers.
  • Suitable functionalized diene rubbers include, but are not limited to, functionalized conjugated 1,3- dienes, for example, butadiene, isoprene, piperylen ⁇ , chloroprene, or mixtures thereof.
  • Suitable functionalized rubbers also include functionalized homopolymers of conjugated 1,3 -dienes and functionalized interpolymers of conjugated 1,3 -dienes with one or more copolymerizable monoethylenically unsaturated monomers, for example, copolymers of isobutylene and isoprene.
  • the functionalized rubber is a functionalized homopolymer of a 1 ,3 -conjugated diene such as functionalized butadiene, isoprene, piperylene, chloroprene, or a functionalized copolymer of a conjugated diene with one or more vinyl aromatic monomers such as styrene; alpha, beta-ethylenically unsaturated nitriles such as acrylonitrile; alpha-olefins such as ethylene or propylene.
  • the functionalized rubber is a copolymer of a vinyl aromatic monomer, then the vinyl aromatic content of the functionalized rubber is less than 30 percent by weight.
  • Other functionalized rubbers include functionalized branched rubbers and functionalized low solution viscosity rubbers. Mixtures of functionalized rubbers can also be used.
  • the functionalized rubber are functionalized homopolymers of 1,3- butadiene.
  • Other non-functionalized rubbers such as linear diene rubbers, diene copolymer rubbers, block copolymer rubbers, for example, styrene-butadiene-styrene block copolymers, can be combined with the highly grafted rubbers used in the rubber modified polymers of the present invention, as long as the advantages of the present invention are still obtained.
  • the functionalized rubber comprises at least 50 weight percent of the total weight of rubber within the rubber modified vinyl aromatic polymer, preferably at least 55 percent, more preferably at least 60 percent, and most preferably at least 65 percent. In one embodiment, the functionalized rubber is used in the absence of any non-functionalized rubbers.
  • the grafted rubber is obtained by grafting the matrix polymer onto the functionalized rubber backbone during polymerization of the matrix polymer. This is accomplished by polymerizing a vinyl aromatic monomer in the presence of a functionalized rubber having at least one functional group per rubber molecule, wherein the functional group is reactive with the matrix polymer under polymerization conditions.
  • the functional group can be any functional group which will react with the matrix polymer to form a grafted copolymer, but is preferably a functional group containing carbon-carbon unsaturation.
  • Typical functional groups include maleates; acrylates, (alkyl)acrylates such as methylmethacrylate, n-propyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate; fumarates, itaconate, citraconate, vinyl ether, vinyl ester, cinnamate, maleimides and derivatives thereof.
  • the functional group does not act as a polymerization initiator or form a stable free radical.
  • the rubber can be functionalized by any process suitable for bonding a functional group to the rubber backbone. Such methods are well known by those skilled in the art. Functionalization typically occurs prior to the addition of the functionalized rubber to the rubber modified polymer polymerization process.
  • the functionalized rubbers are obtained by the incorporation of copolymerizable functional groups in the rubber backbone. These units are typically chosen in such a way that they copolymerize with the vinyl aromatic monomers used to produce the matrix polymer and as such, act as anchor points for the grafting process. Further, these functional groups have a level of reactivity with the vinyl aromatic monomers such that they are substantially reacted, preferably more than 30 percent, more preferably more than 35 percent, and most preferably more than 40 percent, by the time phase inversion occurs. If this level of reactivity is not achieved, the desirable benefits are not realized. If the functional group of the rubber backbone has a high reactivity towards vinyl aromatic monomers, a single functional group per rubber molecule is sufficient. Functionalization using maleate, fumarate, maleimide, acrylate and methacrylate functional groups, typically lead to a polybutadiene chain terminated with a single functional group as exemplified below:
  • pendant vinyl groups can be introduced by reacting the butadiene with a compound having the desired functional groups.
  • the copolymer unit must have sufficient reactivity in order to obtain the desired grafting at phase inversion, or a sufficient amount of such units must be included in order for such reactivity to be attained.
  • the functional group has a low reactivity, then a higher number of groups must be incorporated into the rubber chains such that the desired level of grafting is achieved. As grafting increases, smaller rubber particles are achieved which leads to higher gloss and impact properties.
  • the functionalized rubber has a sufficient number of grafting sites such that a 30 percent level of grafting can be achieved at the point of phase inversion.
  • the rubber is grafted with monovinylidene aromatic polymer to the extent that the amount of grafted rubber is at least 30 percent of the total rubber at phase inversion.
  • the weight average molecular weight (Mw) of the rubber polymer is generally from 10,000 to 600,000, typically from 30,000 to 500,000, preferably from 40,000 to 400,000, more preferably from 45,000 to 400,000, and most preferably from 50,000 to 350,000 as measured by gel permeation chromatography (GPC).
  • Rubber that is, the total amount of functionalized rubber and non-functionalized rubber if present, is typically present in amounts such that the rubber modified polymer contains from 2 to 30, generally from 4 to 25, preferably from 5 to 20, and more preferably from 8 to 20 weight percent rubber, based on the total weight of the monomer and rubber components. The amount of rubber present is also dependent upon the final polymer product desired.
  • the amount of rubber within the rubber modified polymer is from 5 to 15 wt. percent.
  • ABS polymers typically contain from 5 to 30 wt. percent rubber.
  • the term "rubber” or “rubber equivalent” as used herein is intended to mean, for a rubber homopolymer, such as polybutadiene, simply the amount of rubber, and for a block copolymer, the amount of the copolymer made up from monomer which when homopolymerized forms a rubbery polymer, such as for a butadiene-styrene block copolymer, the amount of the butadiene component of the block copolymer.
  • the matrix polymer is a copolymer of styrene and acrylonitrile and the functionalized rubber is a methacrylate functionalized polybutadiene.
  • the weight ratio of styrene to acrylonitrile varies from 99:1 to 60:40.
  • the matrix polymer is polystyrene and the functionalized rubber is a functionalized polybutadiene.
  • the grafted rubber particles typically have a volume average particle size of from 0.01 to 10 microns, depending upon the application.
  • the composition may be monomodal, bimodal or multi-modal depending upon the application as well.
  • the rubber modified polymers of the present invention are produced by a continuous mass polymerization as described in U.S. 4,640,959 combined with in-situ grafting, such that at least a 30 percent, preferably at least a 35 percent degree of grafting is achieved at the point of phase inversion. It is noted that additional grafting may occur after phase inversion, wherein up to 10 or even 20 percent additional grafting may occur. Therefore, rubber modified vinyl aromatic polymers produced by this process would contain functionalized rubbers having at least a 35 percent, preferably at least 40 percent, and up to 100 percent degree of grafting.
  • the mass polymerization can be conducted in the presence of additives such as initiators, chain transfer agents, and lubricants.
  • Typical initiators include peroxides such as t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, 1,1- bis(t-butylperoxy)cyclohexane, benzoyl peroxide, l,l-bis(4,4-di-t-butyl peroxy cyclohexane) propanone; and azo compounds such as azo-bis-isobutyrate and azo bis-cyanovaleric acid.
  • Typical chain transfer agents include mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan, alpha-methylstyrene dimer, l-phenyl-butene-2-fluorene, terpinol, and chloroform.
  • Other additives such as lubricants, for example, stearic acid, behenic acid, stearoamidic acid; oxidation inhibitors, for example, hindered phenols; plasticizers, for example, mineral oil, polyethylene glycol; flame retarding agents, photo stabilizers, coloring agents, fiber reinforcing agents, and fillers can also be used.
  • Solvents may also be employed in the mass polymerization process.
  • Typical solvents include aromatic hydrocarbons such as toluene, benzene, ethyl benzene, xylene, hydrocarbons such as heptane, hexane, and octane.
  • ethyl benzene or toluene are employed.
  • the solvent is employed in amounts sufficient to improve the processability and heat transfer during polymerization. Such amounts will vary depending on the rubber, monomer and solvent employed, the process equipment and the desired degree of polymerization. If employed, the solvent is generally employed in an amount of up to 35 weight percent, preferably from 2 to 25 weight percent, based on the total weight of the solution.
  • the polymerization is conducted in one or more substantially linear, stratified flow or so-called "plug flow” type reactors such as describe in U.S. Pat. No. 2,727,884 or alternatively, in a stirred tank reactor wherein the contents of the reactor are essentially uniform throughout, which stirred tank reactor is generally employed in combination with one or more "plug-flow” type reactors.
  • the temperatures at which polymerization is most advantageously conducted are dependent on a variety of factors including the specific initiator, type and concentration of rubbers, and the co-monomer and reaction solvent, if any, employed. In general, polymerization temperatures range from 60 to 160 °C prior to phase inversion with temperatures from 100 to 190 °C being employed subsequent to phase inversion.
  • a process of grafting the functionalized rubber such that at least a 30 percent, preferably at least a 35 percent degree of grafting is achieved at the point of phase inversion, is also utilized during the polymerization process.
  • Degree of grafting refers to the ratio of functionalized grafted rubber to the total amount of functionalized rubber present. In other words if a functionalized rubber has at least a 30 percent degree of grafting, then at least 30 percent of the functionalized rubber contains at least one grafted chain of matrix polymer.
  • the present invention is a rubber modified polymer consisting essentially of: a) a polymer matrix comprising a polymerized vinyl aromatic monomer, and b) a grafted rubber, dispersed within the polymer matrix in the form of discrete rubber particles containing occluded matrix polymer therein, wherein the grafted rubber is characterized by: i) a degree of grafting of from 30 to 100 percent at the point of phase inversion, ii) an amount of matrix polymer grafted to the rubber of from 20 to 75 weight percent of the total amount of matrix polymer, and iii) being produced by reacting the matrix polymer with a functionalized rubber, wherein the functional group is capable of reacting with the matrix polymer under polymerization conditions, thus grafting the matrix polymer to the rubber.
  • the terms 'consisting essentially of refer to the listed components of the composition and may including minor amounts of other additives which would not significantly alter the physical properties or performance of the rubber modified polymer composition.
  • the rubber modified polymers of the present invention can be used in a number of applications such as housings for small appliances, electronic equipment, and office equipment.
  • the polymerization process used to produce such polymers is an efficient, economical and commercially viable process to produce rubber modified polymers containing highly grafted rubbers which exhibit enhanced physical properties, without the use of additional reactants.
  • a composition containing 51.2 percent styrene, 20.8 percent acrylonitrile, 17.5 percent ethylbenzene and 10.5 percent rubber is fed at a rate of 552 g/hr into the first zone of a stirred tube reactor having a volume capable of holding about 1225 grams of polymer.
  • 50 percent of the rubber is an non-functionalized butadiene-styrene (85/15) block copolymer, 50 percent of rubber is the same composition block copolymer but with a methacrylate end group
  • the reactor is equipped with an agitator set at 120 rpm and comprises three zones, zone 1 being at 107°C, zone 2 at 111 °C, and zone 3 at 116°C.
  • a feed stream containing 0.4 wt. n-dodecylmercaptan, and 1.7 wt. 1,1-di-terbutyl peroxy cyclohexane in 97.9 percent ethylbenzene is added to zone 1 at a rate of 34 g/hr.
  • the polymerization is initiated in zone 1 and continues through zones 2 and 3.
  • zone 3 an additional feed of 2.95 percent n-dodecylmercaptan in ethylbenzene is added at a rate of 30 g/hr.
  • the polymerizing mixture is transferred to a second reactor equipped with an agitator set at 100 rpm and comprised of three zones, zone 4 being at 118°C, zone 5 at 119°C and zone 6 at 123°C.
  • the mixture is then transferred to a third reactor equipped with an agitator set at 30 rpm and comprised of three zones, zone 7 being 131°C, zone 8 at 142°C and zone 9 at 152°C.
  • the mixture is then transferred to a devolatolizer at a temperature of 235°C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne des polymères modifiés par du caoutchouc qui contiennent un caoutchouc fonctionnalisé (c'est-à-dire, hautement greffé) présentant un degré de greffage d'au moins 30 % au point d'inversion de phase et une quantité spécifiée de polymère aromatique vinylique greffé.
PCT/US2004/002890 2003-02-05 2004-02-03 Polymeres modifies par du caoutchouc obtenus a partir de monomeres aromatiques vinyliques Ceased WO2004072137A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AT04707710T ATE455809T1 (de) 2003-02-05 2004-02-03 Kautschukmodifizierte polymere von vinylaromatischen monomeren
EP04707710A EP1592723B1 (fr) 2003-02-05 2004-02-03 Polymeres modifies par du caoutchouc obtenus a partir de monomeres aromatiques vinyliques
BR0406505-0A BRPI0406505A (pt) 2003-02-05 2004-02-03 Polìmeros de monÈmeros aromáticos de vinila modificados com borracha
MXPA05008344A MXPA05008344A (es) 2003-02-05 2004-02-03 Polimeros de monomeros vinilaromaticos, modificados con hule.
US10/542,681 US20060247375A1 (en) 2003-02-05 2004-02-03 Rubber modified polymers from vinyl aromatic monomers
CA002513648A CA2513648A1 (fr) 2003-02-05 2004-02-03 Polymeres modifies par du caoutchouc obtenus a partir de monomeres aromatiques vinyliques
DE602004025203T DE602004025203D1 (de) 2003-02-05 2004-02-03 Kautschukmodifizierte polymere von vinylaromatischen monomeren
JP2006503242A JP2006516672A (ja) 2003-02-05 2004-02-03 ビニル芳香族モノマー由来のゴム変性ポリマー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44552203P 2003-02-05 2003-02-05
US60/445,522 2003-02-05

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WO2004072137A1 true WO2004072137A1 (fr) 2004-08-26

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EP (1) EP1592723B1 (fr)
JP (1) JP2006516672A (fr)
KR (1) KR20050099526A (fr)
CN (1) CN1747977A (fr)
AT (1) ATE455809T1 (fr)
BR (1) BRPI0406505A (fr)
CA (1) CA2513648A1 (fr)
DE (1) DE602004025203D1 (fr)
MX (1) MXPA05008344A (fr)
PL (1) PL377865A1 (fr)
TW (1) TW200528492A (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
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WO2007001916A3 (fr) * 2005-06-27 2007-06-21 Dow Global Technologies Inc Enveloppes a fenetre a films de fenetre lisibles par des lecteurs de caracteres optiques
WO2008130782A1 (fr) 2007-04-18 2008-10-30 Dow Global Technologies Inc. Polymères aromatiques de monovinylidène améliorés comprenant des polymères élastomères fonctionnalisés avec un sulfanylsilane

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US8822597B2 (en) * 2011-04-28 2014-09-02 Fina Technology, Inc. Increasing rubber phase volume in rubber-modified polystyrene
TWI496830B (zh) * 2013-12-26 2015-08-21 Chi Mei Corp 橡膠改質苯乙烯系樹脂、其製備方法及其所製得的成型品
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